SA520412091B1 - Activated spray-dried ziegler-natta catalyst system - Google Patents

Abstract

An activated, titanium-based, spray-dried Ziegler-Natta catalyst system containing a titanium-based Ziegler-Natta catalyst, a carrier material, and an activator mixture comprising an effective amount of an activator mixture comprising triethylaluminum and diethylaluminum chloride for producing a substantially uniform comonomer composition distribution. Also, polyolefins; methods of making and using same; and articles containing same. Fig. 1

Description

ACTIVATED SPRAY-DRIED ZIEGLER-NATTA CATALYST SYSTEM FULL DESCRIPTION BACKGROUND THE INVENTION Titanium-based Ziegler-Natta catalyst with cpolyolefins and methods for its preparation and use; and products containing it. Gllaa (1a primary) Ziegler-Natta (pro)catalysts can be based on titanium 5 or vanadium A typical Ziegler-Natta proto-catalyst comprises a complex of 7:01-MgCla s MgCl is a partitioned solid that has a large surface area and also acts as a carrier.support A typical Ziegler-Natta precatalyst system includes a Ziegler-Natta precatalyst and at least one additional component other than a reducing agent or activator Examples of at least one additional 0 component are an organic Jie organic modifier and a carrier A typical la-nata catalyst system includes a BE la catalyst comprising a reaction product of Jal chemotaxis and chemotaxis; sequentially; For the Zegar-Natta Primary Catalyst System. and then; The Ziegler-Natta catalyst system is prepared by contacting the primary Ziegler-Natta catalyst system with an active reducing agent for the chemical reduction of the primary Ziegler-Natta catalyst system to prepare a chemical reduction product; Then the chemical reduction product was contacted with an activator to increase its catalytic activity and obtain a Ziegler-Natta catalyst system. Clas Ziegler-Natta is cited in the reference The Influence of Mixed Activators on Ethylene Polymerization and Ethylene/1-Hexene Copolymerization with Silica-Supported Ziegler- Natta Catalyst, by 2010,159323-9339 ¢ Nichapat Senso , et al.; Molecules, WIPO 2006/138036a1 and its family members European Office 1891125«0 WIPO 2010/125018a1; and WIPO 2a in Ziegler-Natta catalyst systems « Jom Ziegler-Natta catalyst can polymerize

Olefin monomer(s) olefin monomer(s) organic buffer can attenuate catalytic activity or selectivity catalyst Jie Bl la) dell temperature function or can se combination or reaction activator. The carrier usually determines the size and shape of the Ziegler-protruding catalyst and controls monomer access to it. The function of the carrier can vary from one catalyst system to another based on how the catalyst system is configured; Which in turn largely depends on how the catalyst system is prepared and the composition and characteristics of the carrier.

The support material is a skimmed solid and differs in composition from that of titanium halide and the support material. The carrier may be alumina, clay or ofa silica, the carrier being porous; Mie medium 0 cmesoporous pores and thus can specify outer surfaces (outside the pores) and inner surfaces (inside the pores). Ziegler-Natta catalyst systems comprising a Ziegler-Natta catalyst and carrier Gy can be classified for the characteristics of Jie the size, shape and location of the Ziegler-Natta stimulus, so that these can be controlled

The ag features of the composition of the support material and the method of preparation of the Ziegler-Natta catalyst system. in portable Ziegler-Natta catalyst systems; The carrier can be sald) 5 medium-porous globules of camorphous untreated silica where 1 the inner and outer surfaces are hydrophilic Portable Ziegler-Natta catalyst systems can be prepared; In general by a concentration method comprising a suspension of porous silica in a tetrahydrofuran solution of titanium chloride a glial and magnesium chloride to form cada and then concentrating the mixture by vacuum to obtain a Ziegler-primary catalyst system portable natta” which 0 can be reduced and activated LY. The concentration method is thought to lead to the precipitation of the initial Ziegler-natta catalyst Jala porous silica pores; These are the steps of reduction and chemical activation. The pores contain most or all of the Ziegler-Natta catalyst. Hence, without wanting to be bound by a theory; The porosity of silica is thought to largely determine size and shape; It controls monomer access to the Ziegler-Natta catalyst in portable Ziegler-Natta catalyst systems. during the polymerization processes. Ethylene and/or 5 alpha-olefin can enter porous silica pores in contact with a Ziegler-Natta catalyst and polymer growth can be restricted by the pore medium diameters and pore size. Catalyst systems included

Ziegler-NATA commercial portable UCAT™ A obtained from Univation Corporation

LLC «Technologies «spray-dried Ziegler-Natta catalyst systems In hydrophobic spray-dried Ziegler-Natta catalyst systems, the carrier can be pre-treated fumed silica non-hydrophobic 160 H6-08:C» where the inner surfaces are The exterior is not waterproof. fumed silica 5 Ziegler-Natta spray-dried catalyst systems can be fabricated by a spray-drying method comprising a pre-suspension of hydrophobic silica (pre-treated with a hydrophobic agent) in a tetra dallas silica solution and spray-drying the mixture with cals From the initial Ziegler-Natta catalyst for spray formation of tetrahydrofuran hydrofuran; which can be subsequently reduced and activated. Cine For an initial Ziegler-Natta catalyst system 0 The spray drying method is believed to result in hydrophobic pores containing relatively little or no catalyst (Bl la) which is alternatively stabilized. Therefore, without wanting to be restricted by theory, it is believed that the outer surfaces largely determine the size and shape of the Ziegler-Natta catalyst and control monomer access to it in spray-dried Ziegler-Natta catalyst systems. By contacting ethylene and/or alpha-olefin with a Ziegler-Natta catalyst on the outer surface of the silica the polymer produced on it can grow to a large extent without being restricted by pore dimensions. Commercial spray-dried Ziegler-Natta catalyst systems include UCAT™ J of Univation Technologies LLC. Thus knowledge of supported (primary) Ziegler-Natta catalyst systems is not necessarily predictive or applicable to catalyst systems. Ziegler-Natta (primary) spray-finished; vice versa. As an example of prior technology in this field, US Patent No. 5,290,745; attached to a Ziegler-Natta catalyst system suitable for the production of ethylene copolymers containing a reduced extractable hexane content; Comprising (0) a component of (1) organoaluminum and (b) a component titanium trichloride prepared by reducing titanium tetrachloride with magnesium metal 5 as another example of the technique precedent in this field US Patent No. 5,728,335;

Ally relates to a process for extruding polyethylene having a wide molecular weight distribution where it is prepared to be in the form of granules.” The said extrusion process takes place in a granule extruder having one or more zones primarily filled with polyethylene and two or more zones partially filled With polyethylene Cus cpolyethylene the process involves (1) introducing Jol polyethylene into an extruder at a temperature sufficient to melt the polyethylene ¢polyethylene and (2) introducing a mixture of inert gas and oxygen into each zone is Lia filled with epolyethylene wherein the mixture contains from about 1 to about 21 percent by volume of oxygen relative to the volume of the gaseous mixture; (3) passing molten polyethylene through each zone at Temperature

fusion and (4) extrusion of polyethylene in the form of granules and cooling.

0 GENERAL DESCRIPTION OF THE INVENTION Provides a catalyst system for activated Ziegler-Natta catalysts (BL dines titanium-based “containing (primary) Ziegler-Natta catalysts based on titanium”); a carrier; and an effective amount of an activator mixture comprising triethylaluminum TEAL and diethylaluminum chloride ¢chloride DEAC or an activated reaction product thereof.Innovative catalyst system can be used to enhance the rate of 5 polymerization reaction of a chemical process to manufacture a polyolefin formulation.In said process the effective quantity can be the amount of the activated mixture sufficient to obtain a fairly uniform co-monomer composition distribution (largely flat outline (slightly inclined)) from the ethylene/alpha-olefin copolymer formulations prepared with it. Innovative catalyst on the copolymerization of an ethylene and an alpha-0 olefin copolymer to produce an ethylene/alpha-olefin copolymer composition having a highly uniform co-monomer composition distribution compared to the ethylene/alpha-olefin copolymer produced using a co-catalyst system analogous to the catalyst system Innovative except that the activator of the comparator catalyst system consists of triethylaluminum (TEA) and is free of gla (ethylaluminium chloride) (©0258). The highly uniform co-monomer composition distribution of the innovative ethylene/alpha-olefin 5 copolymer formulation in a system is useful for preparing films with improved mechanical properties. alternatively

or additionally; (Say that the effective quantity is the amount of the activated mixture sufficient to manufacture an innovative ethylene/alpha olefin copolymer formulation that has a high fluidized bulk density FBD and/or a high stable mass density SBD and/or high extrusion effect (thin-film image) for a comparator ethylene/alpha olefin copolymer formulation manufactured using the comparator catalyst system. and/or the inventive extrusion effect of the inventive film layer of an independently elevated ethylene/alpha olefin copolymer composition of at least 665; alternatively at least 9610; and; in some embodiments; at most 9620 for FBD and/or SBD » respectively; of an ethylene/alpha olefin copolymer composition for the comparator and/or the 0 extrusion effect of a film layer of an ethylene/alpha olefin copolymer composition for the comparator; respectively. monomers) (co)olefins;polyolefins prepared by the method; and products manufactured with or made of polyolefin. The polymerization process can be carried out in a gas phase or a liquid phase. Brief Explanation of the Graphics Figure (Fig.) 1 includes parallel plots of changes by weight (% by weight) of the co-monomer contents of the ethylene/alpha-olefin copolymer formulations on the t-axis versus changes in 41 (by GPC) for the ethylene/alpha-olefin copolymer formulations - Olvin on the x penal for each innovation example (B) 5 (A) and comparison example (A) Detailed description: Technical background; disclosure and summary are included for reference here. Specific innovation embodiments are described below as numbered sides For ease of reference, additional embodiments are described elsewhere in this document. Hydrophobic (B) (non-porous).

so far; Alternatively non-porous (WIS) and effective volume activated mixture (C) of TEAL and diethylaluminum chloride (DEAC) in a TEAUDEAC w/w ratio of 80:20 to 20 :80; or an activation reaction product thereof. The effective amount shall be an amount sufficient to obtain a substantially uniform copolymer composition distribution for subsequently prepared ethylene/alpha-olefin copolymer formulations and for the preparation of a polyethylene composition such as an ethylene/alpha-copolymer formulation an olefin; which has a high fluidized mass density and/or a high stable mass density relative to a polyethylene comparator formulation; such as an ethylene/alpha olefin copolymer composition of the comparator; produced by a Ziegler-Natta activator spray-drying-comparator system Activator with TEAL alone or DEAC alone and delivered to the same melting coefficient (12) value as measured by the Melt Index Test Method and the same 0 density value as measured by the Density Test Method described below. The (specified) substantially uniform (narrower) comonomer (CCD) composition distribution of this innovative ethylene/alpha olefin copolymer formulation is an important reason for better physical properties of the formulation. Side 2. Zegar-Natta Activated Catalyst System Dry-Spray and Na-side | where the effective quantity 5 of an activator mixture (©) is 1881/0880 w/w ratio from 25:75 to 75:25; alternatively from 30.0:70.0 to 70.0:30.0; alternatively from 65:35 to 35:65) alternatively from 0.60.0 to 60.0:40.0; alternatively from 45:55 to 45:55 alternatively from 7 to 53:47 alternatively 50:50 Side 3. “Method for Preparation of a Spray-Dried Activated Zegar-Natta Catalyst System” The method comprises a contact of a chemically reduced spray-dried Ziegler-Natta catalyst system comprising a chemically reduced Zegar-Natta (A™) catalyst comprising a complex of ,110 MgCl and hydrophobic pre-treatment fumed silica (8) using the effective amount of activator mixture (©) thus preparing the spray-dried Ziegler-Natta activated catalyst system The activator may comprise one or more alkyl aluminum compounds such as a combination of Diethylaluminum Chloride and Triethylaluminium.The Activation Reaction Can Be Performed Under an Inert Gas 5 Atmosphere and in a Saturated Hydrocurion and/or Aromatic Solvent.As Alkanes; Mixtures of Two SSTs of Alkanes; Mineral Oil; Alkyl Substituted Benzenes as Toluene.” ethylbenzene, or xylene compounds, or a mixture thereof

two or more. The activation reaction can use the reaction mixture prepared in the reduction reaction for the previous side and can be run in the same reactor as the reduction reaction. The resulting spray-dried activated Ziegler-Natta catalyst system can then be introduced to Jolie to polymerize; Such as the polymerization reactor used in the following method for preparing a polyethylene composition. Alternatively, the activation reaction can be carried out in a polymerization reactor; which can be achieved by introducing through a first feed line to the polymerization reactor a first feed stream of a spray dried Ziegler-Natta catalyst system chemically reduced and; separately; Introducing through a second feed line into the polymerization reactor a second feed stream of activator thus preparing the Ziegler-Natta activator spray-dried catalyst system in situ at Ball Jolie where the first and second feed lines are different and their corresponding feed streams enter at different feed points in the reactor polymerization. Alternatively; 0 activation reaction can be achieved by inserting into the co-feed line; which later enters the polymerization Jolie; the first feed stream of a chemically reduced spray-dried Ziegler-Natta catalyst system and the second feed stream of an activator which may begin the manufacture of the spray-dried Ziegler-Natta activated catalyst system in situ in the feed-co-line; Then co-feeding the resulting mixture of the spray-dried Ziegler-Natta catalyst system chemically reduced and activated” (gly-activated catalyst system mentioned was manufactured in the co-feed line; from line 5 co-feed into the polymerization Jolie; thus preparing the Ziegler-Natta activated catalyst system Spray-dried in a polymerization reactor The Ziegler-Natta activated catalyst system can be spray-dried by removing the saturated and/or aromatic hydrocuronic solvent from it without wanting to be bound by theory; we believe that the hydrophobic pre-cured fumed silica outer surfaces largely determine the shape Ziegler-Natta (AT) Catalyst System In the spray-dried activated Ziegler-Natta catalyst system Gay 0 Ziegler-Natta activated spray-dried catalyst system for side 1 or 2 can be a product of method Gg for side 3. A 'spray-dryer' is used in Aspects 1 to 3 In the traditional characteristic field the construction of the LA-Natta (AT) catalyst system in the spray-dried Activated Ziegler-Natta catalyst system is derived from the effects of the preceding step of spray drying; described later. An activated Ziegler-Natta (AT) catalyst has at least 10 times higher catalytic activity and/or polymer yield per unit weight of catalyst than a dose of Ziegler-Natta catalyst

5 Chemically reductive (A) side 4. Method for making a poly(pli) composition The method involves contacting ethylene (monomer) and in form

optional yellow or one; or more (C3-Cao) alpha-olefin (co-monomer(s)) with activated spray-dried Ziegler-Natta catalyst system according to side 1 or 2 to provide a polyethylene composition comprising a polyethylene homopolymer or an ethylene copolymer composition / (C3-Can) alpha-olefin” respectively; and the activator spray-dried Ziegler-Natta catalyst system” or a by-product thereof. The homopolymer of polyethylene includes constituents that are derived from ethylene. The ethylene/(C3-Cao) alpha-olefin copolymer includes monomeric units that are derived from ethylene and copolymers that are derived from one or AST of the (C3-Cao) alpha-olefin monomer(s). ) joint; respectively. The co-monomer constituents derived from (:©-:6) can be alpha-olefins derived from 1-butene; alternatively 1-hexene; alternatively 1-octane; On about 0 alternate a combination of any two of that. Answer 5. The method according to aspect 4 comprises gas-phase polymerization in the presence of molecular hydrogen gas (Ho) and optionally an induced condensing agent ICA in easly two or more gas-phase polymerization reactors under polymerization conditions. (common); Thus manufacturing a polyethylene composition; where (co)polymerization conditions include a reaction temperature from 80 degrees (°) to 5 110 degrees Celsius (°C); Molar ratio of molecular hydrogen gas to ethylene (molar ratio (Hof,©) ranges from 0.001 to 0.050; molar ratio of co-monomer to ethylene du) molarity of co-monomer/(Co) ranges from 0.005 to 0.10. Side 6 The Gay method of side 4 or 5 comprises an ethylene copolymer and one or more (C3-Cao) alpha-olefin (co-monomers) to give a composition of ethylene/(m:©-:2) alpha-olefin copolymer. 0 side 7. Polyethylene composition manufactured by the method according to side 4 5 or 6. Side 8. Synthetic material comprising formed image of polyethylene composition according to side 7. Material can be selected from: [dale] films; wafers extruded material and injection molded material The fabricated material can be a coating layer (eg laminated material) pipe a film layer (eg JO blown film ¢) blown film 5 layer agricultural food packaging food packaging garment bags grocery bags lad) heavy-duty sacks industrial packaging

sheeting pallet and plastic wraps; shrink wraps; bags 585; hoppers cbuckets containers

Freezing “freezer containers” lids clids and toys .toys Side 9. The method according to Side 3 Lad includes an initial step to fabricate a Ziegler catalyst system from a chemically reduced spray drier; The method comprises contacting a spray-dried Ziegler-Natta proto-catalyst system with an active reducing agent for the chemical reduction of a complex of TiCls and:0p thus providing a chemically reduced spray-dried product Ziegler catalyst system; Wherein the spray-dried Ziegler-Natta pre-catalyst system comprises a slurry spray-drying product of a (A+) Bl lay pre-catalyst system consisting primarily of a complex of TiCl3, 148012 and non-hydrophobic pre-fumed dallas silica (5); and optionally tetrahydrofuran. In some respects the titanium complex is made of 11014 and Mg 0 (0p248). In some respects the titanium complex is made of Bl110 and Mg and the component slurry (B) 5 (A*) is made by a first process comprising heating at an initial temperature for an initial period of time +110 and Mg in tetrahydro anhydrous furan for providing a first solution of the complex of TiCls and MgCl in anhydrous tetrahydrofuran; add a finely divided solid, MgCla, to the first solution to provide a suspension of MgCl in the solution of the complex of TICh and anhydrous nitrahydrofuran; 5 heating at a second temperature for a second period of suspended time until the 0p finely divided solid dissolves to provide a second solution of the complex of MgCl g TiCls and addition of 148012 in anhydrous tetrahydrofuran; and adding hydrophobic pre-treated fumed silica (B) to the second solution at a third temperature to provide the slurry of components (A) and (5). In the AT aspects the titanium complex is made of MgCl TiCL.AA “TiC AA” means a mixture of 1:3 molar ratio of Da16/:1101”; which 0 can be obtained from a commercial supplier or can be prepared by reacting 3 mole equivalents of TiCL with 1 mole equivalent of aluminum (Al) metal (AL) serving as the reducing agent. In the AT facets the titanium complex shall be made from a mixture of:HA110 and:A0A118 and the slurry of components (*2) (B)s shall be made by second doles comprising heating at a first temperature and for a second period of time a partitioned solid with a precision of 148012 in anhydrous tetrahydrofuran modifier to provide a third solution of 18612 5 in anhydrous tetrahydrofuran; and adding .7:01 to the third solution at a third temperature and mixing for a first period of time to provide a fourth solution of a complex of TIC AA and 148012 and an additional amount of

(B) in anhydrous tetrahydrofuran; and the addition of pre-treated, non-hydrophobic fumed silica MgCl

to the fourth solution at a third temperature to provide a slurry of components (AY) and (8). Mortar can be mixed

It is made by the first or second process for a third period of time before being spray dried to provide a system

Spray-dried modified Ole Ziegler-Natta catalyst. The appropriate spray drying conditions are described below

In (Sa ABN) the first and second temperatures range independently from 30°C (°C) to the boiling point of the component (©); alternatively from 50° to 65°C;

towards an alternate from 58° to 62° C; Alternatively 60 °C. The first period can range from 10 to 120 minutes; alternatively from 45 to 90 minutes; Alternately from 50 to

dada 0 alternatively 60 minutes. The second time period can range from 1 to 48 hours;

0 alternately from 3 to 30 hours; alternately from 4 to 12 hours; Alternately 5 hours. The third temperature can range from 30° to 55° C; alternatively than

5° to 50° dash alternatively from 35° to 45° C; alternatively

From 40 degrees to 45 degrees Celsius. The third temp can range from 5 to 60 minutes; on

alternately from 10 to 45 dada alternately from 20 to 40 minutes; Alternately 30 minutes.

5 in the first operation; Measured quantities of TICL and Mg metal may be added to a measured amount of anhydrous tetrahydrofuran in a container. for an improved performance of an activated Ziegler-Natta catalyst (87) was eventually synthesized comprising a complex of MgClas TICls (see below); In the first process Ba710 and metal are added

8 and subsequent heating at the first temperature to form the first solution before adding the finely divided solid 148012 to anhydrous tetrahydrofuran. in a variant of the first process; If added

0 finely divided solid 118012 into tetrahydrofuran modifier Sle prior to addition of 11014 and metal Mg to anhydrous tetrahydrofuran; The performance of the ultimately prepared Ziegler-activated (AT)-nata catalyst comprising a complex of 11013 and d14801 (see below) could not be enhanced. be the carrier of the system

Ziegler-Natta activated spray-dried catalyst mainly composed of; alternatively composed of non-hydrophobic, pre-treated fumed silica (8); Which means it has a 0 to 5 weight ratio

5 )% by weight); alternatively zero to 0.9% by weight; alternatively zero to 0.09% by weight; Alternatively zero wt% porous silica. without wanting to be bound by a theory; We think roofs

The non-hydrophilic exterior of pre-cured fumed silica largely determines the construction of the Ziegler-Natta (A) precatalyst in the spray-dried Ziegler-Natta precatalyst system. The reducing agent may comprise trihexylaluminum, diethylaluminum chloride, or, typically; A mixture of trihexylaluminum and diethylaluminum chloride. The reduction reaction may be carried out in an inert gas atmosphere and in a saturated hydrocrionic and/or aromatic solvent; as an alkane; a mixture of two more alkane compounds; mineral oil; Alkyl-substituted Benzene Jie Toluene » Ethylbenzene; or to xylene compounds; or a mixture of two or more. The saturated and/or aromatic hydrocarbon solvent used in the activation reaction can be the same or different from the saturated and/or aromatic hydrocarbon solvent used in the reduction reaction. The resulting Ziegler catalyst system can be chemically dried by removing the solvent

0 saturated hydrochloric acid and/or aromatic thereof. without wanting to be bound by a theory; We believe that the hydrophobic pre-cured fumed silica outer surfaces largely determine the creation of a chemically reduced (AY) Ziegler-Natta catalyst in the spray-dried activated Ziegler-Natta catalyst system. The expression 'spray-dried' is used in these aspects in the traditional domain distinguished where the construction of the spray-dried-activated Ziegler-Natta catalyst system is derived from the effects of the previous spray-drying step.

5 Side 10. The method according to Side 9 also includes a preliminary step for fabrication of the spray-dried Ziegler-Natta precatalyst system; The method comprises spray drying of a mixture of hydrophobic, pre-treated fume silica (8) and a solution of (A) Bl lay precatalyst optionally tetrahydrofuran to provide the spray-dried Ziegler-Natta precatalyst system. The spray-dried (la)-nata precatalyst system according to side 8 or 9 did not come into contact with an active reducing agent for the chemical reduction of a complex of

MgCloy TiCls 0. is a carrier material for the spray-dried pre-catalyst system consisting primarily of; alternatively made up of; Non-hydrophobic, pre-treated fumed silica (8); Which means it has a 0 to 5 weight ratio (70 by weight); alternatively zero to 0.9% by weight; alternatively zero to 0.09% by weight; Alternatively Zero is 96 wt porous silica. without wanting to be bound by a theory; We believe that the non-hydrophobic pre-cured fumed silica exterior surfaces set to an extent

5 Senior Ziegler-Natta Precatalyst Construction (A) Ziegler-Natta Precatalyst System Spray-dried. ala 11. Method Gg of side 9 or 10 is also described by one or more constraints (1)

to (6): (i) titanium chloride is Da710; (2) Titanium chloride is +7:1;

(3) The titanium chloride is a mixture of Wl©11 and Ba1:0; (4) Fume silica shall be treated-

Hydrophobic Ga (B) is a pre-treatment product of untreated fumed silica with

a silicone-based hydrophobic agent; (5) Pre-treatment fumed silica shall be non hydrophobic

5 is a product of untreated fumed silica pre-treatment with a silicone-based hydrophobic agent selected from trimethylsilyl chloride; Dimethyldichlorosilane; Poly Die Fluid

Methylsiloxane"hexamethyldisilane"octyltrialkoxysilane (eg; octyl

trimethoxysilane); and a combination of any two or more of these; (6) Both (2) and (5). Examples of hydrophobic treated fumed silica are CAB-O-SIL hydrophobic fumed silica compounds.

,. Cabot Corporation, Alpharetta Georgia, USA (se available 0

The spray dried pre-catalyst system may be referred to as; Desiccant Ziegler-Natta catalyst system

by spraying, chemically reducing; The spray-dried Ziegler-Natta catalyst system is collectively termed as the spray-dried (primary) Ziegler-Natta catalyst systems. The spray-dried Ziegler-Natta-catalyst system can be characterized as independently modified by one or more of the constraints (1) through (10): (1) Mg atom loading ranging from 2.0 to

5 10.0% by weight (96 by weight); alternatively from 6.0 to 768.5 wt.; alternatively from 6.5 to 968.0 wt.; Based on the total weight of the system that meets the purpose; (2) The concentration of the Mg atom varies

0.82 to 4.11 mmol atom 148 per gram of adequate system (mmol/g);

alternatively from 2.0 to 4.0 mmol/g; alternatively 2.47 to 3.50 mmol/g;

alternatively from 2.67 to 3.29 mmol/g; (3) atom loading Ti ranging from 0.5 to 965.0

0 by weight; alternatively from 1.0 to 704.0 wt.; alternatively from 1.5 to 703.5 wt.; based on the total weight of the system that meets the purpose; (4) The concentration of the Ti atom ranges from 0.10 to 1.04

11 mmol atoms per gram of the system that suffices (Al) mol/g); alternatively than

1 to 0.84 mmol/g; alternatively from 0.25 to 0.80 mmol/g; on about

substituted from 0.31 to 0.73 (Ae mol/g; (5) a Mg-to-Ti molar ratio ranging from

5 (0.79 to 394 alternately from 2.95 to 16.7) (hy) from 3.0 to 15; alternatively from 3.66 to 10.5; (6) Tetrahydrofuran/ethanol rate loading of 15 to

by weight; alternatively from 18 to 70639 wt.; alternatively from 20.0 to 7035.0 wt.; (7) K3 (1) and (2); (8) No (1) and (3); (9) Cad (1) and (4); (10) No (1) and (5); (11) ) No (1) and (6); (12) No (2) and (3); (13) No (2) and (4); (14) No (2) and (5); (15) No (2) and (6); (16) no (3) and (4); (17) no (3) and (5); (18) no (3) and (6); (19) no (4) ( and (5); 5 (20) no (4) and (6); (21) no (5) and (6); (22) no (7) and any one from (8) to (21); ) 23) No (8) and any one from (9) to (21); (24) No (9) and any one from (10) to (21); (25) No (10) and any one from (11) to ( 21); (26) No (11) and any one from (12) to (21); (27) No (12) and any one from (13) to (21); (28) No (13) and any one of ( 14) to (21); (29) no (14) and any one from (15) to (21); (30) no (15) and any one from (16) to (21); (31) no 0 (16) ) and any one from (17) to (21); (32) no (17) any one from (18) to (21); (33) no (18) and any one from (19) to (21); (24) ) No (19) and any one of (20) and (21); (25) No

(20) and (21). The catalyst system of the invention has an improved composition and; optionally; improved body. without wanting to be bound by a theory; It turns out that the improved combination and optionally; The improved conformation is the reason why 5 of the ethylene/alpha olefin copolymer composition of the invention has a fairly uniform copolymer composition distribution (plane diagram). The innovative ethylene/alpha-olefin copolymer formulation demonstrates at least one additional improvement. In some embodiments the Ziegler-Natta catalyst system is characterized by the spray-activated-dried Ziegler-Natta catalyst system of the invention (eg “the spray-activated-dried Bl Ziegler catalyst system of the invention of Inventive Example 1 described below) and the ethylene/alpha-olefin copolymer composition of the invention 0 (eg; the ethylene/1-butene copolymer composition of the invention for the inventive example (A) described hereinafter) synthesized by means of the polymerization method of the invention has at least one of the following scaling property values for the copolymer composition of Ethylene/alpha-olefin analog comparator (eg; ethylene/1-butene copolymer compared to example comparator (A) described below) manufactured using a spray-on Nata Chine play catalyst system UCAT™ J commercial 5 comparator activator for comparator example 1 described Lad after Bg for the same polymerization method: (1) Elmendorf machined tear measured aly at least 110 (alternatively at least 111;) 2 CD rip

7 Sized at least 120) alternatively at least 121 ¢ (3) 2% MD Secant measured at least 4; (4) 2% (4) sles CD Secant Modulus alternatively at least 110¢ at least 111; (5) (ules Dart Impact of at least 105; (6) measured luminosity (45 degrees) of at least 110; alternatively at least 120; alternatively at 5 at least 130 doy at least 135; (7) Optical Haze Measured at most 90 Alternatively at most 80; Alternatively at most 75; (8) Measured Purity of at least 110; Alternatively at least 115; (9) Over The least two from (1) to (8); and (10) each from (1) to

(8). Previous unexpected improvements are embodied in the last 3 schedule. Other things being equal; The innovative Ziegler-Natta catalyst system 0 spray activator innovation (innovative catalyst system) can be used in an innovative polymerization method to manufacture a polyethylene formulation Jie an unpredictable ethylene/alpha olefin copolymer composition that has a high fluidized mass density and/or bulk density A highly stable rather than a comparator formulation manufactured using a spray-dried Ziegler-Natta catalyst system a comparator activator that was activated with an activator composed of triethylaluminum (i.e., lacking diethylaluminum chloride). A high fluidized bulk density FBD 5 is beneficial for performing the polymerization method in a fluidized-bed gas-phase polymerization FB-GPP gas phase reactor configured with a distribution plate to suppress the loss of fine materials from fluidized bed Less amount of polymer particles can be trapped inside the distributor plate obstruction. High FBD Wad helps polymerization reactions use higher resin bed weights; thus providing a high Time Yield STY 06m5 yield; or fluidized mass density per polymer residence time (0) and yield rates. A high stable mass density SBD is useful for storage; transport” and the use of a polyethylene formulation where less anal is required; Nally Jie ST manufacturing output rates can be achieved in pelletizing processes; In equipment with specific dimensions as a forming medium

Gull or pelletizing device. Embodiments of the innovative polyethylene formulation are such as the innovative ethylene/alpha 5 olefin copolymer formulation; which have a regular co-monomer composition distribution to the extent of aS useful on dag especially in the manufacture of thin films from that as it is expected that the produced thin films

Improved mechanical properties due to the highly uniform co-monomer composition distribution. definitions. Composition: Chemical Composition. situation; The type and ratio of atoms in molecules and the type and relative amounts of molecules in a substance. compound: a molecule or group of molecules. concentration: a method of slowly increasing the mass or molar amount of the least volatile chemical constituent(s) per unit volume of a continuous mixture comprising more or less volatile chemical constituent(s). The method progressively removes more of the more volatile component(s) from the less volatile component(s) from the continuous mixture to provide a concentration product with a higher mass or molar amount of the 0 less volatile chemical component(s) per unit volume than the continuous mixture. The concentrate is a precipitated solid. Commonomer composition distribution or CCD: Parallel plot of change in weight percentage of comonomer content (% by weight) or molar ratio (96 in mol) of an ethylene/Wlolefin copolymer composition on the t-axis vs change in (GPC 2) LogM of 5 ethylene/alpha olefin copolymer composition on the -axis”. co-monomer composition distribution; Significantly regular: which has a flat slope CCD (uniform) or raised slightly above or below (extremely uniform (CCD in the comonomer content weight ratio (wt%) or molar ratio) chart % in mol) of the ethylene/alpha olefin copolymer composition on the –” versus change in (GPC 2) LogM for the copolymer composition of 0 for the ethylene/alpha olefin on the – axis”. A perfectly flat line diagram has a slope or gradient (em equals zero (m = zero). The left-to-right superscript line has a slope > zero. The subscript from left to right has a slope of «« < zero. An ethylene/alpha olefin copolymer formulation having a significantly uniform CCD is expected to have improved mechanical and/or optical properties compared to a comparator ethylene/alpha olefin copolymer composition incorporating a regular or conventional CCD. 00131 Composition Distribution Breadth Index. The CDBI value represents the weight ratio of ethylene/alpha olefin copolymer molecules that have a monomer content

Co in the range of 9650 average total molar comonomer content. CDBI dad high Gas indicates that most copolymer particles have a co-monomer content in the range of 1650 for average co-monomer content; which Load indicates that the copolymers of the copolymer are relatively uniform in co-monomer content. The CDBI value is specified for a homopolymer of linear polyethylene that does not include a co-monomer; to be 96100. Methods for calculating 0011 values for copolymers are known in the art; Such as in the World Intellectual Property Organization 03093/93. when the value of 0011 for the first copolymer is higher than the value for the second copolymer; A superscript dad 00131 indicates that the co-monomer distribution of the first copolymer can be more controlled or restricted than the co-monomer distribution of the second copolymer. A copolymer CDBI value of 0 is easily calculated with data obtained from known techniques in the art; like; For example “TREF (temperature rising elution fractionation) is also described; eg” in US Patent 5,008,204 Wild et al., J.

Poly. i .Sci.

Polv.

Phys.

Ed., vol. 20, p. 441 (1982) consisting mainly of; It mainly consists of; and the like. Allows 5 delimited Gia expressions that exclude anything that can affect the base and new properties that otherwise describe them as anything else. consists or consists of. Definite expressions that exclude anything that is not specifically described by the constraints they describe. In some aspects either one can be substituted; Alternately each expression 'consists mainly of' with the expression 'consists of' or 'consists of' respectively. Polymerization (copolymerization): Polymerization of a monomer or copolymerization of a monomer and at least one copolymer. Gel permeability chromatography: GPC is 1772 for Ble for the change in weight ein. 25 Dry Anhydrous Moisture content 0 to less than 5 parts per million on a total parts by weight basis The materials introduced into the reactor(s) during the polymerization reaction are dry.

Effective amount: An amount sufficient to achieve a targeted or significant beneficial result. feed streams. Amounts of reactants and/or reagents that are added to or "introduced" into a Jala reactor. in the continuous polymerization process; Each feed stream can be independently connected or disconnected. volumes or 'feed streams' can be measured; For example; by analogy; Controls the quantities or relative quantities of several reactants and reagents in the reactor at any given time. Membrane: The mentioned film layer properties are measured on 25 μm thick monolayer films. Sb chimney Hydrophobic-pre-treated: untreated fumed silica contact reaction product with hydrophobic agent for reaction with surface hydroxyl groups on untreated 0 fumed silica; Thereby modifying the surface chemistry of fumed silica to provide a non-hydrophobic pre-cured fumed silica. Non-waterproof action can be silicone-based. fumed silica; Untreated: pyrogenic silica produced in flames. consisting of an amorphous silica powder synthesized by incorporating microscopic droplets into a branched agglomeration product; chain-like three-dimensional secondary particles; which agglomerate into triangular particles. Without quartz. Hydrophilic agent: an organic compound or an organosilicon compound that forms a stable reaction product with the surface hydroxyl groups of fumed silica. Induced condensing agent ICA: An inert liquid useful for cooling materials in a gas phase polymerization reactor(s) (eg, fluidized bed reactor). passive: dag is generic; J (significantly) non-reactive or not (significantly) interfering with the reaction 0 polymerization of the invention. The term “inert” as applied to the purge gas or ethylene feedstream means a molecular oxygen content (02) of 0 to less than 5 ppm based on total parts by weight of the purge gas or ethylene feed. LogM is also indicated bLog (molecular weight) and logarithmic molecular weight Mesopore: Has an average pore diameter of 2 to 50 nanometers (nm) 5 Micropore: Has an average pore diameter of less than 2 nanometers Modifier: A composition that Modifies the reactivity; stability; or both of the substances that the composition affects.

Polyethylene: a pdm molecule or a group of Glia macromolecules; It is composed of formative units

0 to 100 mole ratio (mol%); alternatively 70 to 100 mol%; alternatively

0 to 100% in moles” alternatively 90 to 100 96 moles; Alternatively, 95 to 100

6 in moles” alternatively any one of the above ranges where the upper endpoint is >100 ©4 in moles; For said residues derived from ethylene monomer; And the; in aspects where they are

J of 100% in mol ethylene building blocks; The remaining building blocks are units

a co-monomer derived from at least one (C3-Ca0) alpha-olefin; or a group of particles

mentioned huge.

(primary) catalyst: primary catalyst; A catalyst or combination of a precatalyst and a catalyst.

0 quartz: unprocessed crystal image; Microporous silicon dioxide. particulate matter or mass. silica. A particulate form of silicon dioxide that is amorphous. crystalline or gel-like. Includes quartz (rede) fumed silica; silica gel; and gaseous silica gel. Spray Drying: Rapidly forms a particulate solid of least volatile chemical constituents by aspirating a bulk mixture of less volatile and more dols of chemical constituents.

5. Through a spray using hot gas. The particle size and shape of the particulate solid formed by spray drying can differ from that of the precipitated solid. System: An interconnected arrangement of different chemical components so as to form a function as a whole. Transfer: movement from one place to another. Movement from reactor to reactor (doles tank to reactor; reactor to tank) and manufacturing unit to storage facility and vice versa.

0 Ziegler-Natta (primary) catalysts and Ziegler-Natta (primary) catalyst systems. See technical background for general description. All of the above dag forms in Jah fall into the heterogeneous category of (primary) Ziegler-Natta catalysts and systems because they form solid-phase olefin polymerization reactions in a gas- or liquid-phase. Material . tonic. The activator may comprise an alkyl (C1-Ca) aluminum compound. can include

5 Aluminum compound containing (b©-.0) alkyl groups 1 2 or 3 (C=C) alkyl and 2 1 or zero groups each independently selected from the 5 (C1-Ca) chloride atom . maybe you can be

Each C1-Cy alkyl independently is methyl;ethyl;propyl; 1-methylethyl;butyl; 1-methylpropyl; 2-methylpropyl; or 1,1-dimethylethyl. Each can be (C= C) An alkoxide independently is a methoxide, ethoxide, peroxide, 1-methyl ethoxide, butoxide, 1-methylpropoxide, 2-methylperoxide, or 1,1-dimethylethoxide.It can be an aluminum compound containing (©-,© ) alkyl tri-jil aluminum (TEA) tricthylaluminum triisobutylaluminum ¢ (TIBA) triisobutylaluminum diethylaluminum chloride (DEAC) chloride diethylaluminum ethoxide (TATAS) ethylaluminum dichloride (EADC) or a combination or mixture of any two or more of the above The inhibitor may be triisobutyl 0 aluminum (TIBA) Diethylaluminum chloride ((DEAC) diethylaluminum ethoxide (DEAE) or ethylaluminium dichloride (EADC) ll (C3-Cao) olefin. Compound with formula ([):-8 1:0-001] 0 where is a straight string USI group (C1-Cis). The (©-©) alkyl group is a monovalent unsubstituted saturated hydrocrion having from 1 to 18 carbon atoms. Ble RAd 5 is about methyl; Ji propyl; butyl; Pentyl Hexyl; Heptyl » Octyl » Nonel; decel; Unidecyl; Dodecyl; tridecyl; tetradecyl; pentadecyl; hexadecyl; hypotadecyl; and octa-decyl. In some embodiments the (H:0-:2) alpha-olefin is 1-propene 1-butene; 1-hexane; or 1-octane; alternatively 1-butene, 1-hexene; or 1-octane; alternatively 1-butene or 1-hexene; alternatively 1-butene or 1-octane; alternatively 1-hexene or 1-octane; on 0 towards substituent 1-biotin; alternatively 1-hexene; alternatively 1-octane; alternatively a combination of any two of 1-butene, 1-hexane; and 1- octane. carrier substance. prior to treatment with a hydrophobic agent; The carrier is uncured silica with a variable surface area (pang) mesosome. in some embodiments”; The surface area ranges from 50 to 150 square meters per gram (m/g). The average particle size 5 can be less than 1 micrometer (µm). Each of the above properties is measured using traditional techniques known in the art. Untreated silica can be amorphous silica (without

quartz); alternatively amorphous silica; Alternatively, fumed silica. These silica compounds are commercially available from several sources. Silica can be in the form of spherical particles; which are obtained by spray drying processes. Untreated silica may be calcined (ie » dehydrated) or uncalcined prior to treatment with a hydrophobic agent. Liethylene: compound with formula HoC=CHy hydrophobic agent; Silicon-based: An organic silicon compound that forms a stable reaction product with hydroxyl groups on the surface of fumed silica. The Ble organosilicon compound can be an organic dimeric siloxane or an organosilicon monomer; which includes silicon-bonded leaving groups (eg (Jad) 51:5-halogen groups; 58:0-oxime (>©011-0-:5); 5:-alkoxy" or 5:-amino) which react with hydroxyl groups on the surface of untreated fumed silica to form Si-O-Si bonds with the loss of a water molecule as a by-product. Includes a poly-bio-organic siloxane complex; as polydimethylsiloxane; Main chain of groups (0-5-:58 where Sa) The oxygen atom forms a stable hydrogen bond to the surface hydroxyl group of a fumed silica. A silicone-based hydrophobic agent can be trimethyl 5mCl; dimethyldi chlorosilane; fluid polydimethylsiloxane”hexa die diesilane” octyltrialkoxysilane (eg” octyltrimethoxysilane);and combination of two or more thereof.An induced thickening agent or ICA in some respects is ICA is substituted (Cs-Ca0) alkane cost (C11-Ca0) substituted (Cs-Cio) alkane 0 in some respects ICA is 0 for (29 ©:0) an alkane In some respects (C5-Cio) an alkane is a pentane, eg, natural-pentane or isopentane; hexane; heptane; octane; nonane; decane; or a combination of any two or more In some respects ICA is isopentane (ie, 2-methylbutane). The innovative method of polymerization using CA may be referred to herein as an inert condensation mode process (1040). 5 Concentration in the gas phase using gas chromatography by calibration of the peak area to mole ratio (mol%) using a gas mixture meter for known concentrations of gas phase constituents that are adequate for the purpose. The concentration can range from 1 to 10 96 moles; alternatively

From 3 to 8 96 mol. The use of ICA is optional. in some respects; including some of the inventive examples described below; CA is used as an example” in aspects of the method of making mixtures of ICA catalyst can be introduced into a polymerization reactor. in other aspects of the method; The use of (ICA) can be omitted and a dry preformed catalyst may be introduced mixed as is in Jolie polymerization; in which ICA deficiency is a reducing agent. A substance that is effective for the chemical reduction of a complex of 11013 (Ti) MgClas Agent can be used Reducing in a chemical reducing effective amount; that is, an amount that is effective to form a chemical reducing product but is not sufficient to activate the same reducing complex of TiC and D[1480. The reducing agent can be tri-alkyl aluminum such as trihexylaluminium; and dialkyl 0 aluminum halide as diethylaluminium chloride or, typically, a combination of trialkyl aluminum and dialkyl aluminum halide as a combination of trihexylaluminum and diethylaluminium chloride (primary) Ziegler-Natta catalyst systems spray dried dng generic. Each of the modified spray-dried Ziegler-Natta (pro)catalyst systems has catalytic activity in the Bale piled polymerization reactions Photoactivated has more catalytic activity and greater polymer yield than that of the corresponding photo-5 precatalyst All conditions are equal; can vary The catalytic activity and polymer yield of these reactions from embodiment to embodiment of an activated spray-dried Ziegler-Natta catalyst system. Such variations are within the normal skill range of operators in the art to control (Sarg) depending on the specific formulation and form of the activated spray dried Ziegler-Natta catalyst system. Relevant formulation factors include Mg g Ti loadings and a molar ratio of Mg to Mg dad) Ti 08-p. 708). Relevant 0 modulation factors include average initial particle size; initial particle size distribution; agglomeration and particle shape or agglomeration product of the Ziegler-Natta catalyst particles. The previously described carrier and catalyst system preparation method also determine the forming factors mentioned. Spray-dried (primary) Ziegler-Natta catalyst systems can be general; independently as a dry powder, suspension or slurry in a saturated hydrocarbon and/or aromatic solvent. The saturated and/or aromatic hydrochloric solvent 5 can assist in the treatment of the (primary) catalyst system. The saturated and/or aromatic hydrocarbon solvent can be an alkyl-substituted benzene or alkane (toluene or

xylene). DAG (primary) Ziegler-Natta catalyst systems can be operated independently; Synthesis Reaction Reduction; activated; modified; treat them; stored; and transported in conditions suitable for the intended purpose. These conditions include deli conditions, storage conditions, and transportation conditions. These general dag adverbs are well known in the field. For example, the spray-dried (primary) Bl la catalyst systems can be made in the form of (Jie), manufactured, glial reaction, activated, modified, handled, finished, stored, transported in an inert atmosphere, die gas composed of anhydrous He No and/ or Ar and/or in a saturated hydrocuric and/or aromatic solvent such as those described herein.These conditions may include well known techniques for these systems Jie technologies.Schlenk line 0 polymerization types Ziegler catalyst system can be used Spray-dried nata in Bal olefin reactions in gas phase or liquid phase to enhance the rate of polymerization of monomer and/or co-monomer(s).Liquid phase reactions include a slurry phase and a solution phase.In some aspects the olefin polymerization reaction is performed in the phase le alternatively liquid phase; alternatively slurry phase; bay (bay) solution phase. 5 Conditions for the gas phase and liquid phase olefin polymerization reactions are generally well known. pall The conditions for the olefin polymerization reactions in the gas phase are generally described The following gas polymerization reactors sha) can be polymerized at high pressure liquid-phase or gas-phase polymerization reactor to provide polyethylene of the invention Composition The said reactors and methods dag are generally well known in the field. For example 0 torrents » The liquid phase reactor/polymerization method can be a solution phase or a slurry phase as described in US Patent 3,324,095. The gas phase polymerization method/reactor can use stirred-bed gas-phase polymerization reactors (SB-GPP reactors) and fluidized-bed gas-bed polymerization reactors (SB-GPP reactors). (fluidized-bed gas-phase polymerization reactors (FB-GPP reactors) and an induced condensation agent can be performed in a condensation mode polymerization such as described in US Patent 4,453,399 ¢ US Patent 4,588,790; US Patent 4,994,534; US Patent

5,352,749 US Patent 5,462,999; And American patent 6,489,408. The gas phase polymerization reactor/method can be a fluidized bed reactor/method as described in US Patent 3,709,853; US Patent 4,003,712; US Patent 4,011,382; US Patent 4,302,566; US Patent 4,543,399; US Patent 4,882,400; US Patent 5,352,749; US Patent 5,541,270; European Office - I - 0 802 202; And the Belgian patent No. 839,380. The cited patents disclose gas phase polymerization processes where the polymerization medium is mechanically stirred or fluidized by a continuous flow of gaseous monomer and a diluent. Other expected gas-phase processes include multi-stage combinations or polymerization processes such as those described in US Pat. 5,627,242; US Patent 5,665,818; US Patent 5,677,375; 0 European Office-A- 0 794 200; European Office-B1- 0 649 992; European Office-

A- 202 802 0; and EMCT-B-634421. In an illustrative embodiment the polymerization method utilizes a gas-phase polymerization of a pilot fluidized bed reactor (Pilot Reactor) comprising a slog of an ethylene/alpha-olefin powder copolymer fluidized bed reactor and a plate. wis placed on the lower head; locate a bottom gas inlet; 5 includes a cardio sector or cyclone system; at the top of the reactor vessel to reduce the amount of particulate resin that can escape from the fluid bed. The expanded sector defines a gas outlet. The Pilot Reactor also includes a pressure bellows of sufficient capacity to circulate and vortex the gas continuously from outside the gas outlet in the section expanding in the gall of the reactor vessel downwards and into the lower gas inlet of the Pilot Reactor and through the distribution plate and fluidized bed. The Pilot Reactor also includes Cooling System 0 to remove the heat of polymerization and maintain the fluidized bed at a target temperature. Gas compositions such as ethylene are monitored; alpha-olefin » hydrogen; and oxygen introduced into the Pilot Reactor by parallel gas chromatography in the cycle loop to maintain specific concentrations that determine and enable the control of polymer properties. In some embodiments the "ays" of the gases are formed causing the temperature to drop below the dew point for the time in question the Pilot Reactor is in condensation mode (CMO) 5 operation or an induced condensation mode operation (ICMO) In the CMO the fluids are located under the cooler and in the lower head under the distribution plate. The activated spray dried Ziegler-Natta catalyst system can be introduced as a slurry

on Cals powder inside Pilot Reactor from high pressure devices; The slurry is introduced through a syringe pump and the dry powder is introduced through a graduated disc. The catalyst system typically enters the fluidized bed in the lower third of its bed height. The Pilot Pilot Reactor also includes a fluidized bed weighing method and Jie (Product Discharge System) ports for discharging a powdered ethylene/alpha-olefin copolymer from the reactor vessel in response to increasing fluidized bed weight as the polymerization reaction proceeds. polymerization conditions (co-)polymerization conditions i.e. the result of an active variable or combination of these variables; like a catalyst formula; amount of reactant; molar ratio of two reactants; absence of overlapping subjects (eg 0 » 11:0 and :0); or a process variable (eg “rate or temperature of the feed stream)” step; or a sequence which is efficient and beneficial to the copolymerization method of the invention in the polymerization reactor(s) to provide the polyethylene of the invention in combination. At least one can be installed; Alternatively each of the (co-)polymerization conditions (ie; unchanged) during the production of polyethylene of the invention is a composition. The fixed (co-)polymerization conditions 5 may be referred to in this case as the steady-state (co-)polymerization conditions. Steady-state (co)polymerization conditions are advantageous for achieving continuous polyethylene embodiments of the invention having a composition having the same properties as the polymer. alternatively At least one can be diversified; Alternately two or more (co)polymerization conditions in their specified operating variables during production of the polyethylene composition of the invention so as to proceed from production of a first embodiment of the polyethylene composition of the invention having a first set of polymer properties to a non-inventive polyethylene composition or of a second embodiment of the polyethylene composition of the invention having a second group of ADSL properties) wherein the first and second groups of polymer properties differ and each is within the limits described herein for the polyethylene composition of the invention. For example, all other (co)polymerization conditions are equal; A high molar ratio of 5 ll (C3-Cao) olefin/ethylene co-monomer feed streams in the invention's method of copolymerization yields a low density polyethylene composition of the resulting product of the invention. Moving from group to group is allowed

other than (co)polymerization conditions within the meaning of '(co)polymerization conditions' where the operating variables for both sets of (co)polymerization conditions are in the ranges specified for them in this document. A useful consequence of the previous transition is that any described property value of a poly formulation can be achieved Ethylene for the invention by those of ordinary skill in the field in the light of the instructions contained in this document.

The (co)polymerization conditions for gas or liquid phase reactors/methods can also include one or more additive Jie Chain Transfer Agent; enhanced or scavenging agent. The chain transfer agents are well known and may be an alkyl metal such as diethyl zinc. The enhancers are well known as in 4,988,783 (US) and may include chloroform; CFCI3; trichloroethane;

0 Run slurry or gas phase polymerization processes without (not intentionally added) scavenging agents. The (co-)polymerization conditions for quantitative Load gas phase polymerization reactors/processes (eg » 0.5 to 200 ppm based on all feed streams within a reactor) can include fixed controls and/or continuity additives such as aluminum stearate or Polyethylene Imene. Static control agents may be added to the gas phase reactor to discourage the formation or build-up of a static charge in it.

(Sa 15) that Lad (co)polymerization conditions include the use of molecular hydrogen to control the final properties of a polyethylene formulation. The use of Hy is generally described described in Polypropylene Handbook 76-78 (Hanser Publishers, 1996) All other things being equal, ag of hydrogen can use molten flow rate (MFR) for melting coefficient (MI) cal where MFR or MI is affected by hydrogen concentration.The molar ratio can range from hydrogen

0 to the total monomer (Ha monomer); hydrogen to ethylene (HYCo) or hydrogen to co-monomer (“/:11-olefin”) from 0.0001 to 10; alternatively 0.0005 to 5; alternatively 1 to 3; Alternatively 0.001 to 0.10.

The (co)polymerization conditions can include a partial pressure of ethylene in the polymerization reactor(s) independently from 690 to 3450 kPa (100 kPa) to 500 psi

5 insq absolute o(psia) alternatively 1030 to 2070 kPa (150 to 300 psi absolute); Alternatively 1380 to 1720 kJ (200 to 250 lb

per square inch (absolute); alternatively 1450 to 1590 kPa (210 to 230 psi absolute); For example (Jd) 1520 kPa (220 psi absolute). 1,000 pounds per square inch absolute = 6.8948 kilopascals. In some respects the gas phase polymerization is performed in a fluidized bed-gas phase polymerization reactor FB-GPP 5 under fluidized bed-gas phase polymerization conditions; for the relevant gas phase. Such conditions are any variable or combination of variables that can affect the polymerization reaction in the FB-GPP reactor or the composition or property of an ethylene/alpha-olefin copolymer product made with this process. Variables can include reactor pang design; catalyst composition and quantity; the composition and amount of the reactant; molar ratio of two different reactants; the presence of 0 or β Ho Jie feed gases and/or 02” molar ratio of the feed gases versus the reactants; Absence or concentration of interfering substances (eg “absence or presence of induced AES factor” (FRO) (ICA) mean residence time of the polymer (avgPRT) in the reactor; partial pressure rates of components; feed rates of monomers” degree The temperature of the reactor bed (for example, the fluidized bed temperature); the nature and sequence of the process steps; the transition times between the steps. In the procedure of the method of the invention, variables other than those described or changed by the method of the invention may be kept constant. The molar ratio of a gas may vary Co-monomer/ethylene 0/02 of co-monomer and ethylene introduced into the FB-GPP reactor from 0.0001 to 0.1; alternatively from 0.0002 to 0.05; alternatively from 0.0004 to 0.02.The partial pressure of ethylene in the reactor can range - FB-GPP from 690 to 2070 kPa (kPa” i.e. 100 to 300 psi absolute (psi absolute)); alternatively from 830 to 1655 kPa (120 to 240 psi (dane absolute); alternatively from 1300 to 1515 kPa (190 to 220 psi absolute). Alternatively, the partial pressure of ethylene can range from 690 to 3450 kPa (kPa). ; 100 to 500 psi absolute (psi 5 absolute)); alternatively 1030 to 2070 kPa (150 to 300 psi absolute days); Alternatively 1380 to 1720 kJab (200 to 250 psi

absolute); alternatively 1450 to 1590 kPa (210 to 230 psi absolute); For example, “Jal is 1520 kPa (220 hay per square inch absolute). 1.000 psi absolute = 6.8948 kPa. The molar ratio of hydrogen gas to ethylene (H2/C2) in the FB- GPP 5 reactor can range from 0.0001 to 0.025 alternatively from 0.0005 to 0.200; alternatively from 0.149 to 0.009 alternatively from 0.009 to 0.109; Alternatively from 0.010 to 0.100. Oxygen concentration (02) for parts by volume of ethylene (©: OY 02 per million parts by volume of ethylene) (ppmv) in the JFB-GPP reactor Typically; oxygen is not targetedly introduced 0 into the reactor ©2-00 In some embodiments the reactor 73-0017 is free to a greater degree than 0; eg »/d0 is from 0.0000 to 0.0001 ppm vol; alternatively 0.0000 ppm vol. The temperature of the reactor bed can range in the FB-GPP reactor from 90° to 120°C; alternately from 95° to 115°C; alternately from 99° to 5 110°C; alternately from 100.0° to 109°C; Alternatively from 0° to 89° C. Average Polymer Residence Time (avgPRT) Number of minutes or hours on average settled polymer product in the -FB-GPP reactor avgPRT can range from 30 minutes to 10 hours; Alternately 60 min to 5 hours Alternately 90 min to 4 hours Alternately 0 1.7 to 3.0 hours Pay gas phase reactor or polymerization method restart includes start or restart of the FB-GPP reactor Restart (cold start) or sale) start the FB-GPP reactor Restart (warm start) the period of time before the steady state polymerization conditions of step (a) are reached. Operation or restart can involve the use of a preloaded or loaded 5 polymer core layer; respectively in a fluidized bed reactor. The polymer core layer may consist of a polyethylene powder such as a polyethylene homopolymer or an ethylene/ethylene copolymer.

Alpha-olefin. Starting (or sale) of the FB-GPP reactor can also include atmospheric gas transitions that also involve purging air or other unentrained gas(s) from the reactor using a dry (anhydrous) inert purge gas; followed by purge with an inert purge gas obtained from the FB-GPP reactor with dry ethylene gas. Sle dry inert purification can consist primarily of molecular nitrogen (0); argon » helium; or a mixture of any two or more. dlls not running; before starting (cold start)»; The FB-GPP reactor contains an atmosphere of air. The dry inert purge gas can be used to purge air from a recommissioned FB-GPP reactor during early start-up stages to provide an FB-GPP reactor with a dry inert purge atmosphere. before sale) run 0 (ie, before the change in crystallization strata); FB-GPP Jolie can include an unwanted ICA atmosphere or another unwanted gas or vapor. The dry inert purge gas can be used to scavenge steam or unwanted gas from the FB-GPP Jolie transition during early restart stages to provide the FB-GPP reactor with a dry inert purge gas atmosphere. Any Jala purge gas itself can be flushed from the FB-GPP reactor with dry ethylene gas. Dry ethylene 5 may also include molecular hydrogen gas such that the dry ethylene gas is introduced into a fluidized bed Jolie as a mixture thereof. Alternatively dry molecular hydrogen gas may be introduced separately and after the fluidized bed reactor atmosphere transitions to ethylene. Atmospheric gas transitions can be made prior to; coll or after heating the FB-GPP reactor to the polymerization temperature for the polymerization conditions. Starting or restarting the FB-GPP reactor also involves introducing feed streams of 0 reactants and reagents into it. The reactants include ethylene and an alpha-olefin. The reagents introduced into the fluidized bed Jeli include molecular hydrogen gas, an induced thickening agent (ICA), and an activated spray-dried-Zigler-Natta catalyst system. A compound includes all naturally available isotopes and isotopic rich forms of it. Rich images can have medical or anti-fake uses. In some aspects it can be any compound; ASH format; dad or reaction product herein is free of any of the chemical elements selected from the group consisting of:

<H Tt “Be Say 0” O “N Till” Mg “Na Y” Cl ¢S < P ¢Si Each “Ca on 1 k” Mn “Cr ¢V “Nb” Zr ¢Y “Sr”Rb “Br”Se ¢As “Ge”Ga “Zn”Cu “Ni”Co “Fe Shell “Rh”Ru “Tc”Pd in “Cd Mel <Te “Sb” Sn L “Cs only” “Os” Re “¢W “Ta”Hf on ¢Au “Pt on” TI BiPb lanthanoid; actinoids; The band does not exclude the chemical elements coated by the compound; combination; formula; The mixture or reaction product (eg, ©Hg required by a polyolefin or ©;11,0 required by an alcohol). Catalyst Yield: Calculated in kilograms of (co)polymer resin manufactured per kilogram of catalyst used (kg copolymer/kg catalyst” or; hase “kg/kg”). The calculation per kilogram of catalyst is based on the amount of titanium in the polymer as Measured by 0 X-ray fluorescence spectrometry (‘Ti IXRF’) or by coupled plasma photoemission spectrometry (“Ti ICPES’) Gia Catalyst yield can be expressed as a range of kg/kg (defined as Ti (IXRF to kg/kg (defined by ICPES 11) Purity test methods: ASTM D1746-15 Standard Test Method for Transparency of Plastic Sheeting Expression of results in 5 images Percentage (96) of transition.Dart Impact Test Method:Dart Impact Measured Gy to ASTM D1709-16a, Standard Test Methods for Impact Resistance of Plastic Film by «Free-Falling Dart Test Method LA Method A uses a thread with a ~38.10 + 0.13 mm (1.500 + 0.005 in) diameter hemispherical head dropped from a height of 0.66 0.01% ie (26.0 + 0.44 in). 0 Said test method can be used for diaphragms for which impact resistors are required to have masses of about 50 g or less to about 6 kg for crushing. Results are measured in grams (g). Density Test Method: Measured lg to ASTM 792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B Example; in 2-liquid prolyol). Record the results in grams per cubic centimeter (fon cm?). Elmendorf Tear Test Method Gg is standardized to ASTM 1922-09, Standard Test Methods for Propagation Tear Resistance of Plastic Film and Thin Sheeting by Pendulum Method,

8 (fixed radius). (Luis equivalent to 6383-2 150.) Record results as tear measured in counter direction (CD) or instrument direction (MD) in gram-force (gf) Film Puncture Test Method: ASTM 05748 — 95( 2012), Standard Test Method for Protrusion Puncture Resistance of Stretch Wrap Film. The probe is coated with polytetrafluoroethylene and has an outer diameter of 5 cm (0.75 in). The overlay is fixed during the test. The probe eventually pierces or breaks through the fixative membranous layer. dad is recorded as the force at fracture i.e.; maximum strength; power (operation) to break or penetrate the fixed diaphragm; And the distance that the sensor penetrates when breaking using a program

0 mechanical test. The probe gives a biaxial stress on the clamping diaphragm that exemplifies the type of stress encountered by diaphragms in a number of product end use applications. Said resistance is a measure of the energy absorption capacity of the membrane to resist puncture under these conditions. Results are expressed in ft-pound-force per square inch (ft*lbs per ft/inch?).

Flow coefficient test method (190°C; 21.6 kg; ".:11): Uses ASTM Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion ,101238-13 (Platometer using conditions of 190°C/21.6 Kilograms (kg).Record results as lang filtered sequentially grams per 10 minutes (g/10 minutes) or equivalent in decigrams per 0 minutes (dg/1 minute).

190° Flow Rate Test Method (Augie 5.0 kilograms (kg)); (I) for measuring an ethylene based (co)polymer according to D1238-13 8511/1 using conditions of 190°C/5.0 kg; formerly known as 'BE conditions Wad is defined as 1. Record the results as sequentially filtered grams per 10 minutes (g/10 minutes) or equivalent in decigrams per 1.0 minutes (dg/1 minute).

Flow rate ratio test method (190°C; ''15/:d1'): Calculated by dividing the value obtained from the flow coefficient test method Dy by the value obtained from the unitless flow rate Iss test method.

Test Method Fluidized Mass Density (FBD) Defined as Weight of Solids Per Bang Volume of Fluidized Bed Specific Surface Gas Velocity (SGV) (Uncorrected) = (5 * “(ST'H)/(AP) where AP is the pressure drop between the underscore and middle dash in pounds per square inch (psi” or psi); 5 is the cross-sectional area of the reactor in square inches (in); 51 is the cross-sectional area of the reactor in dreaded feet (ft”); and 11 is the distance between the bottom and middle bars in feet (ft). FBD (uncorrected) is corrected to an actual value (FBD (corrected)) based on reactor pressure, temperature, and gas density 7. FBD units can be converted

(corrected) to kilograms per cubic meter (ofa) Gel permeability chromatography (600): Average molecular weight test method: Select My 0 average molecular weight number (.24); Mo/Mas using chromatograms obtained on a high-temperature gel transmittance chromatography (HTGPC, Polymer Laboratories). Laboratories PLgel 10 µm 0160-3 all contained in an oven maintained at 0°C The method uses he component BHT-treated 708 with a nominal flow rate of 5 1.0 milliliters per minute (mL/min) and a volume of A nominal injection of 300 μl (µl).The solvent was prepared by adding 6 g of biotinylated hydroxytoluene (BHT (an antioxidant)) in 4 liters (l) of reagent grade 261 4-trichlorobenzene (¢) TCB) and filter the resulting solution through a 0.1 micrometer (µm) Teflon filter to save the solvent. Degas the solvent using a parallel degassing device before entering the ©111010 apparatus. Calibrate the columns using a set of 0 (05) monodisperse polystyrene meters. separately Prepare known concentrations of test polymer dissolved in solvent by heating known amounts of it in known volumes of solvent at 0°C and shaking for 2 hours to provide solutions. (measure all volumes by gravimetric analysis) target solution concentrations; co of the test polymer for 0.5 to 2.0 milligrams of polymer per milliliter of solution (mg/mL); with low concentrations; co used for high molecular weight copolymers 5. Before running each sample; Purge the DRI reagent and increase the flow rate in the device to 1.0 mL/min/; and allow the DRI reagent to settle for 8 hours before injecting the sample

The first. Calculate My My using international calibration relations with column titres. Calculate MW at

each size of the sequential filter using the following equation:

log, = m oma + Gps +1 logM mm - a, +1 a, +1

where the lowercase letters “JX” refer to the test sample, the lowercase letter “75” denotes Wii 20.0 Kis 70000175 a, and 9 Kb is obtained from the published field. For polyethylene compounds » 0.695/0.000579 = Ka/Rh. For polypropylene compounds = K/L 8 At each point in the resulting chromatogram, calculate the “concentration” “” of the DRI signal subtracted from the initial value (pry using the following formula: Cua© = KpRyIpRIAdn/de) 1 is a constant defined by the DRI calibration / denotes pled) and 0/ 00 is a

0 is the increase in the refractive index of the polymer. for polyethylene” = dn / de 0.109. Calculate the polymer mass extraction from the ratio of the combined area of the concentration chromatogram to the lysate volume and injection volume equal to a predetermined concentration multiplied by the cyclic injection volume. Record all molecular weights in grams per mole (g/mol) unless otherwise noted. Details of the methods for determining “My” are also described (My 111770 in 2006/0173123 US pp. 24-25) paras [0334].

to [0341]. Plot (MW)dW/dLog on the y-axis against (MW)Log on the x-axis to provide a Gus “GPC” chromatography plot of which is (MW)dW/dLog s (MW)Log As specified above.

Melt flow ratio (190 °C) (L/L) test method: Calculated by dividing the value obtained from the alae flow test method:1, by the value obtained from the DA test method for the melting coefficient. Without unit .

Melting coefficient test method (190 °C; 2.16 kilograms (kg); '.1'): For ethylene-based (co-)polymer measured in accordance with 171238-13 (ASTM using conditions of 190 °C/2.16 kg; formerly known B 'BE conditions' aka: 1. Record the results as sequentially filtered lang grams per 10 minutes (g/10 minutes) or equivalent in decigrams per 0 minutes (deci [aha 1 minute]. 10.0 - 0 1.00 g The melting coefficient is inversely proportional

5 with an average molecular weight of polyethylene; Although the inverse proportion is not linear. Subsequently; whenever

molecular weight increased; The melting point decreased. Optical Luster Test Method: ASTM 2457-13, Standard Test Method for Specular Gloss of Plastic Films and Solid Plastics Measure luster using a glossometer at incidence angles of 20°–45°; 60 degrees»; or 75 degrees. The sparkling shine is without a unit. Photohaze test method: ASTM 101003-13, Standard Test Method for Haze Luminous Transmittance of Transparent Plastics 00e. Measure the haze with a haze meter. Express the haze as the transmission rates of luminosity which, when passing through the stratum corneum, are deflected from the incident light ray by forward scattering. Results are expressed as a percentage (96). 1 5 2% Cut Modulus Test Method: Measured Gy to ASTM 0882-12, Standard Test for Tensile Properties of Thin Plastic Sheeting 0 1111005. Uses either 961 or 962 cut modulus in reverse (CD) Or Machine Orientation (MD) Record the results with MPa 0 psi Jha = 6.8948 MPa. Stabilized mass density (SBD) test method determined as the weight ratio of a material per unit volume. SBD is measured by gravity decanting of an amount of polymer resin to an overflow of a cylinder of 5 empty weight 400 cubic centimeters (an) after removing the excess amount of polymer resin by sliding a straight edge across the top of the cylinder. The resulting plane of a complete cylinder is weighed; The empty weight of the cylinder is subtracted; The weight of the resulting resin is divided by the volume of the cylinder to give an SBD of pounds per Fs. This value can be converted to pounds per cubic foot (lb/ft) or to kilograms per cubic meter (kg/m). Tensile Modulus Test Method: Measured to Uy 882-12 Standard Test Methods ¢ASTM for Tensile Properties of Thin Plastic Sheeting Record results in contra-direction (CD) as mean strain at yield in percent (%) or Mean alga) at yield in MPa or in the machine direction (MD) as average strain at yield (96%). 1,000.0 psi d (psi) = 6.8948 MPa. 5-Diethylaluminum Chloride: Obtained from Albemarle Corporation. magnesium dichloride: carrier; Obtained from SRC Worldwide Inc

Magnesium Metallic Flakes (Aldrich Chemical (Grignard-Aldrich) Flakes: Hydrophobic Fumed Silica 1: Carrier; Low Surface Area Fumed Silica activated with dimethyldichlorosilane obtained as 15-610 from Cabot Corporation. Anhydrous Tetrahydrofuran: Organic Modifier; Obtained from Pride Chemical Solution-Titanium Tetrachloride: Obtained from WR Grace Titanium Trichloride m/: Obtained from WR Grace Triethylaluminium: activator; obtained from Albermarle or Akzo (gl hexylaluminum : reducing agent; obtained from Albermarle or denatured. Also known as tri-“-hexylaluminum or TnHal.

0 1-Biotin (“04”): co-monomer; Used with a molar ratio of 2©/4© in Tables 1 and 2. Ethylene ("2©"): monomer; used at a partial pressure of 62 in Tables 1 and 2. Isopentane: induced condensation agent 1 (10817); used at a mole percentage concentration (96 mol) in the gas phase of a gas phase reactor with respect to molar content Total Sal phase material in Tables 1 and 2. Hydrogen gas (“HL”) da used with a molar ratio of 112/02 in Tables 1 and 2.

5 Preparation 1: Synthesis of a spray-dried Ziegler-Natta proto-catalyst system modified by tetrahydrofuran. Add tetrahydrofuran GeV (28 kg) to the feed tank. Next add TiCls (530 grams (g)) and Mg metal (36 g). Heat the resulting solution to 60 °C; And mix it saad an hour to confirm the first solution. Then add a finely divided solid MgCl (1340 g) and mix at 60 °C for 5 hours overnight to dissolve the MgCl and make a second solution. Once dissolved and 0480 cool the solution

0 second to 40°C to 45°C then add pre-cured non-hydrophobic fumed silica «Cabosil TS-610 (1.7 kg) to provide suspension. Mix the suspension for 30 minutes to provide a slurry of a modified Ole Ziegler-Natta catalyst system and non-hydrophobic pre-cured fume silica. Spray the slurry in a spray dryer using the following conditions: inlet temperature sha 160°csi outlet temperature 110°C; feed rate of approximately 45 kg per hour; Total gas flow is close to 270 kg

5 per hour; Atomizer speed: Variable typically by about 9685 to provide the pre-catalyst system Ziegler-Natta modified pre-catalyst modified spray-dried pre-catalyst for 1.

Preparation 11 (inferential): Synthesis of a spray-dried Ziegler-Natta proto-catalyst system modified by tetrahydrofuran. Add anhydrous tetrahydrofuran (28 kg) to the feed tank. Then add a finely divided solid MgCl (1255 g). Preheat the mixture to 60 °C; Mix it for 5 hours overnight to form a third solution. Cool a third solution of 40° ge to 45° C. then add TICIAA (459 g); And mix for an hour. Then add Hydrophobic Pre-cured Fumed Silica “Cabosil TS-610” (1.6 kg) to provide a suspension. Mix the suspension for 30 minutes to provide a slurry of a modified Ole Ziegler-Natta catalyst system and non-hydrophobic pre-cured fume silica. Spray the slurry in a spray dryer using the spray-drying conditions of a [Ziegler-catalyst] preparation to provide the initial catalyst system.

Dried Nata-Primary Modified Spray-dried Modified For Preparation A

0 Preparation 2 (actual) or 2 (deductive): Synthesis of a spray-dried Ziegler-Natta primary catalyst system; Reductant modified by tetrahydrofuran. Schal contact spray modified Ziegler-Natta primary catalyst system (china) was prepared by a graded version of a preparation of 1 (actual) or 1 (deductive) with a working amount of a chemical reducing agent of a reagent mixture of 9640 wt trihexylaluminum ( TnHAI) reducing agent in mineral oil in a 4 liter (L) mixing tank for about an hour to provide reaction mixture; Then add

5 Reagent mixture of 9612 wt diethylaluminum chloride (©018) in mineral asphalt to the reaction mixture and mix for an additional hour to provide a spray-dried Ziegler-Natta catalyst system for the 2 or 2 2 reducing preparation; respectively. The molar ratio of 101181 to DEAC is approximately 0.875/ 1.000. Inventive Example 1 (IED (actual) or 1a (Ela) deductive): Synthesis of the spray-dried Ziegler-Natta catalyst system modified with tetrahydrofuran. Contact procedure for a spray-dried Ziegler-Natta catalyst system

0 reductant of preparation 2 (actual) or 2 (deductive) with 25:75 (w/w) co-introduced mixture of activators (gla ethyl aluminum chloride (DEAC) and triethylaluminium TEAL) or (TEAL in cu) metal within the reactor by either co-feeding to the bed or by co-feeding within the gas cycle line to provide a spray-dried activated Ziegler-Natta catalyst system for 151 or 1a; respectively. Inventive example 2 (152, actual) 125 (d152, deductive): similar to 181 or Ela respectively;

5 Except that the DEAC/TEAL weight/weight ratio is 40:60. Comparative Example 1 (051): Repeat TET shal except using an activator consisting of Ya TEAL from the mixture

activator; To provide the spray-dried activator Ziegler-Natta catalyst system for the 051. TEAL is introduced into the reactor by either the inlet-to-bed or inlet-to-gas-cycle line. Inventive Example M (8(15)): Copolymerization of ethylene and 1-butene catalyzed by a spray-dried activator Ziegler-Natta catalyst system to provide an ethylene/1-butene copolymer composition. Preparation 2 is fed into the reactor as a slurry of metallic Cu. Preparation 2 is fed into the reactor through a first feed stream and a 75/25 weight/weight ratio of DEAC/TEAL mixture is fed into the polymerization reactor through a second feed line” where the first and second feed lines are different. The ethylene/1-butene L(18)8 copolymer composition is produced in a single gas phase polymerization reactor with a production capacity of 15 to 25 kg resin per hour. For the trial session; Preload the reactor before starting with a 0 crystallization layer of granular resin inside. Dry the crystallization bed reactor to less than 5 ppm (igh) using high purity nitrogen. Then introduce the reaction component gases; ethylene » hydrogen; f-1-biotin; to the reactor to form a required gas-phase composition as Led below in Table 1. Simultaneously heat the reactor to the required temperature. Once the (co)polymerization conditions are reached; Inject a feed stream of a slurry of 17 96 wt. of a spray-dried Ziegler-Natta catalyst system 5 (modified by tetrahydrofuran) for preparation 2 in mineral oil into the reactor through a first feed stream line. Simultaneously, a 27/75 w/w DEAC/TEAL mixture is fed into the polymerization reactor through a second feed line where the first and second feed lines are different. Use about 5 to 5 layer changes to achieve steady-state production of an ethylene/1-butene copolymer composition; It thus provides the embodiment of TE(A)'s innovative ethylene/1-butene copolymer structure. Collection of the innovative 0-ethylene/1-butene copolymer formulation from the reactor product discharge outlet. Inventive Example B (8(18)): Similar to TE(A) except that preparation 2 is introduced into the reactor as a slurry of metallic Cu. Preparation 2 is fed into the reactor through a feed stream line Jf and a 40/60 w/w mixture of 0280/1181 is fed into the polymerization reactor through a second feed line where the first and second feed lines are different. 5 Comparative Example ((e)68): Copolymerization of ethylene and 1-butene etched by the Ziegler-Natta catalyst system spray-dried activator comparator of CEL to provide an ethylene/1-butene copolymer composition. repeat

Inventive example A except using 71/81 as an activator but not ©01280. Reactor conditions are shown

and process later in Table 2. Collect the ethylene/1-butene conjugate copolymer composition from

Reactor product discharge outlet.

Innovative copolymer formulations of ethylene/1-butene copolymer can be distinguished for TE(A) and IE(B) and the

Comparative copolymer of ethylene/1-butene for CE(A) comparator to CD- «MD-Stress © Yield

«2% MD Secant Modulus <Elmendorf CD Tear ¢<Elmendorf MD Tear «Stress © Yield

Clarity (45 degree) Gloss “Dart Impact “Film Puncture” 2% CD Secant Modulus

and photohaze using the corresponding test methods mentioned earlier. Comparative properties can be measured

to differentiate CE(A) accordingly by scoring it as equal to 100. (Kar) Measure the inventive properties of the TE(B) 5 IE(A) 0 features independently with respect to the corresponding comparative properties of the CE(A) discrimination by dividing Valuable

inventive characteristic; And multiply the result by 100. For CD-Stress © «<MD-Stress © Yield

% CD 2 Wii MD Secant Modulus? «Elmendorf CD Tear «Elmendorf MD Tear» Yield

Gloss “Dart Impact “Film Puncture ¢”Secant Modulus (45°)” and “Clarity” are the measured values.

Al over 100 is an improvement versus L100 for optical haze.” The measured value is 5 less than 100 Bai vs. 100.

Table 1: Gas Phase Copolymerization Reactor/Process Conditions for E(B) 5 (A)IE

M12 DEAC/TEAL (w/w) 0 to 17200 kg/kg Table 2: Process Conditions/Gas shal copolymerization reactor for slab.

M Ziegler-Natta L-B Sprinkler System 0 EY (Ji 1 CE1: Commercial UCAT™ J TEAL = only) 27 Catalyst Yield (kg/kg) 0 to 184 800 kg Stable Mass Density (kg/cm ? ) 225360[3a] fluidized AS density (kg/cm?) 199 [22S m3 as indicated by the data in Tables 1 and 2; Innovative Ziegler-Natta activated spray dried catalyst systems for TE2 5 TET produce ethylene/alpha-olefin copolymer formulations of TE(A) and 8(18), respectively” that have unexpectedly high fluidized mass densities and density ratios. Stable mass higher than the corresponding mass density ratings of the ethylene/alpha olefin copolymer formulation (CEA 5) comparator produced using the Ziegler-Natta catalyst system spray dried activator comparator for CET Table 3: Properties of the ethylene/alpha olefin copolymer formulations 1-Biotin for <IE(A) «CE(A) and (s)12. duals Polymer IE(B) IE(A) CE(A) Density (ASTM D792-13) g/cm 5 091977 09192 Fusion coefficient L (190°C; 2.6 kg; 2.03 1.98 1.84 “(ASTM D1238-04 g/10 min. Flow rate Is (90 1 °C; 5.0 kg; 5.81 5.61 5.24”) (ASTM D1238-04 g/10 min. FL flow coefficient, ( 190°C; 216 kg; 54.0 51.0 47.8” (ASTM D1238-04 g/10 min. OM) me 5 Oo) 5 me

Mean molecular weight number o(My) g/mol 25.910 25136 | 25746 Average Weight ad (.14); g/mol 7 103.004 | 103.347 As shown by the data in Table 3 or Figure 1,” the ethylene/1-butene A copolymer of the JE(A) innovator and by the association of the Ziegler-Natta catalyst system with the spray-dried activator 1 of the JE1 innovator show improvements Large in co-monomer composition distribution (CCD).

Claims (5)

protection elements 1. An activated spray-dried Ziegler-Natta catalyst system comprising an (A*) activated Ziegler-Natta catalyst comprising an activated complex of titanium trichloride titanium trichloride TiCls and magnesium chloride MgCl hydrophobic pre-treated fumed silica 5 (5); an effective quantity of an activated mixture (©) of triethylaluminum TEAL and tdiethylaluminum chloride DEAC or an activation reaction product thereof; wherein the effective amount of the activated mixture (C) is tri-Ji aluminum (sloftriethylaluminum diethylaluminum chloride) at a w/w ratio of 75:25 to 25:75. 2. Method of fabrication of the activated spray-dried Ziegler-Natta catalyst system in accordance with claim 1; The method involves contacting a reduced spray-dried Ziegler-Natta catalyst system comprising a reduced Ul lay (A™) reduced Ziegler-Natta catalyst comprising a chemical reduction product of a chemically reduced complex of titanium trichloride TiCls, magnesium chloride, and hydrophobic pre-treated fumed silica (5); using the effective amount of activated mixture (©); Thus, Ziegler-Nata catalyst system was prepared by spraying activated spray .dried Ziegler-Natta catalyst system 3. A method for preparing a polyethylene composition The method comprises the contact of an ethylene monomer and yellow; One; Or a group of comonomers of alpha-olefin with from 3 to 20 carbon atoms with an activated spray-dried Ziegler-Natta catalyst system according to the element protection 1; To provide a polyethylene composition comprising a polyethylene homopolymer (LIU) or an ad gyfethylene copolymer of alpha-olefin having 3 to 20 carbons, respectively” and a catalyst system cactivated spray-dried Zicgler-Natta catalyst system or a by-product thereof. 4. The method according to claim 3 comprises a gas phase polymerization in the presence of molecular hydrogen gas Ha and one SICA-induced condensing agent or a combination of gas phase polymerization reactors polymerization 35 under (co)polymerization conditions; Thus manufacturing a Cus ¢polyethylene formulation The (co)polymerization conditions include a reactor temperature of 80°C to 110°C; molar ratio of molecular hydrogen gas to ethylene monomer 1 to 0.050; The molar ratio of one or a group of co-monomers of an alpha-olefin with 3 to 20 carbon atoms to the ethylene monomer is from 0.005 to 0.10. 5. The method according to claim 3 comprising the copolymerization of an ethylene monomer and one or a group of alpha-olefin co-monomers having from 3 to 20 carbon atoms to provide a polyethylene composition polyethylene comprising an ad gyfeethylene covalent alpha-olefin having from 3 to 20 atoms of carbon Figure + gx 1 oe EB (IEA) *: 4 6 4 1 . 1 CEA) CER) » Ro'eraz 7 1 A ; 3 a * SN j \ $y pi yl afm 1 Re © i, . F % 3 Fa a bo 4 < 3 #8 (tn) and § x and ab nt. a % = 3 3 we \ 1 ¥ = § YON 3 To J i § \ . Jr Log {ast Sl Chromatography Nod 3} The Saudi Authority for Intellectual Property Sweden Authority for Intellectual Property pW RE .¥ + \ A 0 § Um 5 + < Ne ge “Benaj > Aye Ki Jada Li Days TEE Bbha Nase eg + Ed - 2 - 3 .++ .* provided that the annual financial fee is paid for the patent and that it is not null and void due to its violation of any of the provisions of the patent system, layout designs of integrated circuits, plant varieties and industrial designs, or its implementing regulations. »> Issued by + BB 0.B Saudi Authority for Intellectual Property > > > “+ PO Box 1011 .| for ria 1*1 uo ; Kingdom | Arabic | For Saudi Arabia, SAIP@SAIP.GOV.SA